Metal hydride nanoparticles

ABSTRACT

A nanoparticle of a decomposition product of a transition metal aluminum hydride compound, a transition metal borohydride compound, or a transition metal gallium hydride compound. A process of: reacting a transition metal salt with an aluminum hydride compound, a borohydride compound, or a gallium hydride compound to produce one or more of the nanoparticles. The reaction occurs in solution while being sonicated at a temperature at which the metal hydride compound decomposes. A process of: reacting a nanoparticle with a compound containing at least two hydroxyl groups to form a coating having multi-dentate metal-alkoxides.

TECHNICAL FIELD

The disclosed materials and methods are generally related to metal andmetal-hydride nanoparticles.

DESCRIPTION OF RELATED ART

Generally the currently used materials for metalizing of energeticformulations are micron scale aluminum particles. The main problemsassociated with the burn properties of the traditional metal additivesin energetic formulations have to do with the burn kinetics/speed beingimpeded by the aluminum oxide coating of the particles which arisesnaturally from the materials being exposed to air. The nanoscale Almaterials with various passivators for energetic formulations have beenexplored on an experimental basis (Berry et al., “Synthesis andcharacterization of a nanophase zirconium powder” J. of Mat. Chem., 13,2388-2393 (2003); Jouet et al., “Surface Passivation of Bare AluminumNanoparticles Using Perfluoroalkyl Carboxylic Acids” Chem. of Mat., 17,2987-2996 (2005); Jouet et al., “Preparation and reactivity analysis ofnovel perfluoroalkyl coated aluminum nanocomposites” Mat. Sci. Technol.,22, 422-429 (2006). All publications and patent documents referencedthroughout this nonprovisional are incorporated herein by reference.)

Larger scale synthesis of air and moisture sensitive metal nanoparticlesis a challenge, and poses an obstacle to investigating the physicalproperties of the nano-scale materials via traditional techniques thatexpose the materials to air. To obtain materials that do not oxidizewhen handled in air while still retaining their properties, the surfaceof the nanoparticles can be protected by a passivating agent. In orderto keep the intrinsic properties of the unpassivated material, it isdesirable to maximize the active metal content of the material whileminimizing the amount of passivator present on the nanoparticle surface.

Synthesis of metal and alloy powders at high temperatures can imparthomogeneity, crystallinity, and stability; however, some applicationsbenefit from heterogeneity and amorphous metals due to their increasedreactivity. For example, amorphous/nanocrystalline borides showincreased activity as dehydrogenation catalysts and battery anodes overtheir crystalline counterparts. {Li, 2012 #213; Liu, 2014 #209; Mitov,1999 #272; Zhao, 2013 #271}. Along with being active dehydrogenationcatalysts, Ti—B alloys are also attractive as metal fuels andpropellants due to their low cost and high volumetric energy density.{Dreizin, 2009 #50; Galfetti, 2006 #38; Wen, 2010 #137} Hydrogen is alsoa coveted chemical energy storage medium, but suffers from lowvolumetric energy density. Hence, a material comprised of metallic Ti—Band hydrogen could mitigate the low volumetric energy density intrinsicto hydrogen while increasing the overall energy density of the Ti—B,thereby producing a reactive, high energy density material.

BRIEF SUMMARY

Disclosed herein is a process comprising: a reacting Ti(BH₄)₃ withLiAlH₄ in an aprotic solvent while being sonicated to producenanoparticles comprising titanium, boron, and hydrogen; and annealingthe nanoparticles under a vacuum.

Also disclosed herein is a process comprising: reacting a transitionmetal salt with an aluminum hydride compound and a borohydride compoundto produce one or more nanoparticles comprising decomposition productsof the aluminum hydride compound and the borohydride compound. Thereaction occurs in solution while being sonicated at a temperature atwhich the aluminum hydride compound and the borohydride compounddecompose.

BRIEF DESCRIPTION OF THE DRAWINGS

A more complete appreciation of the invention will be readily obtainedby reference to the following Description of the Example Embodiments andthe accompanying drawings.

FIG. 1 shows SEM micrographs of material 4 (Example 4) showing theblurring that occurs at higher magnification (bottom) as compared tolower magnification (top)

FIG. 2 shows TEM micrographs of material 3 (Example 3). Top: largeparticle enveloped in metal-alkoxide; Center: a population of smallnanoparticles on carbon background; Bottom: lattice fringing observedfrom nanoparticle overhanging on edge of carbon grid.

FIG. 3 shows material 5 (Example 5) initially (top) and after 24 h indH₂O (bottom)

FIG. 4 shows ²⁷Al-NMR of material 2 (Example 2) annealed at 89° C. underdynamic vacuum overnight (top) vs. ²⁷Al-NMR material 5 (bottom).Asterisks denote spinning side-bands.

FIG. 5 shows general synthesis conditions and proposed reactionmechanism for Ti—B—H powders.

FIG. 6 shows an X-ray diffraction pattern for Ti—B powder heat treatedat 720° C.

FIGS. 7A-F show scanning electron microscopy images of Ti—B powders heattreated at 150° C. (FIGS. 7A and 7D), 425° C. (FIGS. 7B and 7E), and720° C. (FIGS. 7C and 7F).

FIG. 8 shows TGA traces for Ti—B powders at a heating rate of 25° C./minunder a 60% 02 atmosphere.

FIG. 9 shows MS (m/z=44) traces for Ti—B powders at a heating rate of25° C./min under a 60% 02 atmosphere.

FIG. 10 shows DSC traces for Ti—B powders at a heating rate of 25°C./min under a 60% 02 atmosphere.

FIG. 11 shows TGA-MS and DSC traces for as prepared Ti—B powder underargon atmosphere.

DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS

In the following description, for purposes of explanation and notlimitation, specific details are set forth in order to provide athorough understanding of the present disclosure. However, it will beapparent to one skilled in the art that the present subject matter maybe practiced in other embodiments that depart from these specificdetails. In other instances, detailed descriptions of well-known methodsand devices are omitted so as to not obscure the present disclosure withunnecessary detail.

Disclosed is a homogeneous solution-based method used to producewell-defined passivated air and moisture stable transition metalaluminum/boron/gallium hydride nanoparticle materials. The synthesis maybe accomplished via a multi-step process. A transition metal salt isreacted with an aluminum hydride compound, a borohydride compound, or agallium hydride compound. The reaction occurs at a temperature at whichthe resulting transition metal hydride compound decomposes. For example,ZrCl₄ or Zr(BH₄)₄ may be reacted with LiAlH₄ at room temperature.Zr(AlH₄)₄ is produced, which decomposes at room temperature. The metalhydride compounds can contain hydrogen-bridging bonds, which may breakduring decomposition. This results in the loss of some, but notnecessarily all of the hydrogen in the nanoparticles in the form ofhydrogen gas. The use of sonication in solution may cause nucleation ofthe decomposition products so that nanoparticles are formed.

Suitable transition metals in the transition metal salt include, but arenot limited to, zirconium, hafnium, titanium, vanadium, scandium,yttrium, niobium, chromium, tantalum, thorium, or uranium. Reaction of ahafnium salt with a borohydride may produce HfB₂ as a decompositionproduct, which has a particularly high volumetric heat of combustion.

The nanoparticles may be annealed after they are formed. Annealing canconvert amorphous material into crystalline material, and may drive offsome or all of the remaining hydrogen. It may also cause reaction ofsome or all of any unreacted salts remaining in the nanoparticles. Theannealing may be performed under vacuum at a temperature that is up tofrom about one third to one half the melting point (Kelvin) of thedecomposition product in order to drive the dehydrogenation reaction tocompletion and further nucleate and/or crystallize the particles.

In a next step, a coating is formed on the nanoparticle by reacting itwith a compound containing at least two hydroxyl groups to form acoating comprising multi-dentate metal-alkoxides. Suitable compoundsinclude, but are not limited to, glycerol, sorbitol, and a carbohydrate.

The coating may be in the form of a xerogel from heating the reactionfollowed by drying in a vacuum, which causes shrinkage of the gel andpossible entrapped solvent. The aluminum or other metal can act as acrosslinking site for formation of the coating, as aluminum can bind to6 oxygen atoms. The process may pull some aluminum or other metal atomsfrom the surface of the nanoparticle and into the coating.

A coating made from glycerol, a small molecule, may be relatively thicksince the growing gel coating is more permeable for addition of moreglycerol—a relatively small molecule The thicker coatings may bedesirable for gas permeable applications where the fraction of reactivemetal is less important. Larger compounds such as sorbitol may form athinner coating, which may be desirable for maximizing the reactivemetal content for applications such as energetic materials. Theresulting material may be air and moisture resistant/stable, and containupwards of >90% of active metal by mass, and may be used as a metalizingadditive for energetic formulations.

The same type of coating may also be formed on other types ofnanoparticles that contain a metal that reacts with hydroxyl groups toform a metal-alkoxides. Suitable nanoparticles may contain aluminum,boron, silicon, zirconium, or hafnium, for example.

The initial reaction to produce the zirconium aluminum hydride was viadecomposition of zirconium tetrahydroaluminate (Zr(AlH₄)₄) while exposedto ultrasound produced by a benchtop ultrasonic bath. The particles weresurface passivated using carbohydrates and were shown to be stable inair and partially stable in water. TEM imaging suggests the existence ofsmaller particles made of a Zr—Al alloy that range in size from 1.8 nmto 7.9 nm in diameter and are interspersed with larger particles thatrange from tens to hundreds of nanometers in diameter. It was also shownthat the carbohydrate-derived coating of the nanoparticles is present asan aluminum alkoxide gel surrounding the core particles.

Based on the initial characterization of materials 1-5 (Examples 1-5),these materials have been shown to contain mainly Zr and Al, and thepassivated versions of these materials are robust and are air andmoisture stable. Based on the elemental analysis results, in the bestcase, Zr and Al constitute more than 90% of material 5. It has also beenshown that by varying the size of the carbohydrate that was used as thepassivator it is possible to change the amount of passivator remainingon the surface of the nanoparticles. Based on the TEM images of thelarger particles, combined with EDS data, it is possible to suggest amodel for the structures that is cocoon-like. The cocoon shell consistsof interlinked multi-dentate metal-alkoxides that form a polymeric shell(aerogel) that surrounds the metal-hydride particle.

This method can produce particles of smaller size that are moisture andair stable, which will enable better burn properties. This method can beextended to other higher density transition metals, such as Hf, Ta, Th,and U, which would produce much higher density materials, giving themunitions that carry it greater momentum while retaining the sameburn/shock wave characteristics as the lighter metals currently used.

Also disclosed is a room temperature approach to the gram scaleproduction of hydrogen-loaded amorphous solid-solution titanium-boronpowders. The advantages of using this low temperature synthesis methodare two-fold: 1) the low temperature catalytic decomposition of Ti(BH₄)₃to elemental Ti and B is incomplete and results in retained hydrogen; 2)the low reaction temperatures prevent the alloying of the Ti and B tothermodynamic Ti—B crystal phases. Trapping the Ti and B in athermodynamically unstable state and retaining hydrogen increases theenergy stored in the powders. {Trunov, 2008 #192}{Epshteyn, 2009 #260;Epshteyn, 2013 #215}

The solution synthesis of Ti—B powders has been reported via thegeneration of Ti(BH₄)₃, followed by thermal decomposition to TiB₂.Ti(BH₄)₃ is formed in solution by adding an alkali metal borohydride(commonly Li or Na) to TiCl₄ in an ethereal solvent, under air freeconditions. {Bates, 1995 #203; Chen, 2004 #189; Gu, 2003 #190; Jensen,1988 #207} The TiCl₄ is reduced to the Ti(III) oxidation state by oneequivalent of BH₄ ⁻, while the other three equivalents of BH₄ ⁻substitute the remaining chlorides. H₂ and B₂H₆ gasses, as well as LiClsolid byproducts are formed. The Ti(BH₄)₃ is unstable at roomtemperature and is reported to undergo autocatalytic decomposition anddehydrogenation on the order of days. {Hoekstra, 1949 #204} Hence,thermal decomposition is commonly used to impart stability and formTiB₂. {Bates, 1995 #203} Here, LiAlH₄ is used to initiate the partialdecomposition of Ti(BH₄)₃ at room temperature under sonication. Usingthis approach to induce only partial decomposition is important toretain hydrogen that is preserved over extended time scales in theamorphous product. A schematic for an example proposed reactionmechanism is shown below. The process is shown schematically in FIG. 5.

1TiCl₄+4LiBH₄→1Ti(BH₄)₃+4LiCl+0.5B₂H₆ (g)+0.5H₂ (g)

1Ti(BH₄)₃+0.1LiAlH₄→Ti—B—H (powder)+B₂H₆ (g)+H₂ (g)

At least the second step above is performed in an aprotic solvent whilebeing sonicated, followed by annealing the nanoparticles under a vacuum.The molar ratio of Ti(BH₄)₃ to LiAlH₄ may be, for example, from 1:1 to1,000,000:1 or from 1:1 to 12:1. Suitable aprotic solvents include, butare not limited to diethyl ether, acetonitrile, toluene,tetrahydrofuran, dimethyl ether, any solvent in the glyme series, anddioxane. The solvent may be one that can solubilize Ti(BH₄)₃ and LiAlH₄.

The sonication may be performed at, for example, −15° C. to 97° C. orroom temperature (such as 20° C. to 25° C.). The anneal may be performedat, for example, 50° C. to 2000° C., 500° C. to 900° C., 700° C. to 750°C., or 700° C. to 2000° C. The vacuum may have a maximum pressure of 10,100, or 1000 mTorr, with a maximum ppm of water and/or oxygen of 2, 5,or 10.

The resulting nanopowder may comprise at least 90 wt. % elementalamorphous titanium and elemental amorphous boron, and further maycomprise no more than 5 wt. % of total crystalline titanium or boron,alloyed titanium and boron, and titanium-boron compounds.

The following examples are given to illustrate specific applications.These specific examples are not intended to limit the scope of thedisclosure in this application.

General—All air and moisture sensitive manipulations were performed in aVacuum Atmospheres glove box under an atmosphere of helium or viatraditional Schlenk technique under an atmosphere of nitrogen. Drydiethyl ether (Et₂O) was purchased from Aldrich packaged under nitrogenin a SureSeal bottle, and was used without further purification.Glycerol was purchased from Aldrich and was vacuum distilled prior touse. Lithium aluminum hydride (LiAlH₄) was purchased from Aldrich andwas further purified by dissolution in Et₂O, followed by vacuumfiltration and removal of volatiles in vacuo. Lithium borohydride(LiBH₄) and zirconium (IV) chloride (ZrCl₄) was purchased from Aldrichand used as provided. Zirconium borohydride (Zr(BH₄)₄) was prepared aspreviously reported in literature (Reird et al. J. Electrochem. Soc.,104(1), 21 (1957)). Oxygen bomb calorimetry was performed using a Parrmodel 1341 Oxygen Bomb calorimeter with a model 1104 Oxygen CombustionBomb. Microanalysis was performed by Complete Analysis Laboratories,Inc. SEM imaging was performed using a LEO 1550. TEM imaging wasperformed using a JEOL 2200FS, equipped with a Gatan Ultrascan chargecoupled device (CCD) camera. ²⁷Al-NMR was performed on a Bruker DMX500at 11.7 T.

Example 1

Synthesis of material 1 from ZrCl₄ and LiAlH₄—From a 200 mL Schlenkflask a clear solution containing 665 mg of LiAlH₄ (LAH) in 80 mL ofEt₂O was transferred dropwise via cannula over 2 h to a round-bottom 300mL storage flask fitted with teflon valve joint, which contained 1.02 gof ZrCl₄ suspended in 100 mL of Et₂O being sonicated in ice-water in aVWR 50HT benchtop ultrasonic cleaning bath. Upon initial addition awhite precipitate appeared in solution, producing a white slurry. Oncethe addition was completed, the flask was closed with a Kontes Teflonvalve and allowed to sonicate overnight at −50° C. (ultrasonic bathoperating temperature) producing a black slurry. Volatiles were thenremoved in vacuo and 1.81 g of solids was isolated. The material wasplaced into a Pyrex sublimator and heated to 340° C. under dynamicvacuum. 1.66 g of the product black powder 1 was isolated.

Example 2

Synthesis of material 2 from Zr(BH₄)₄ and LAH—From a 200 mL Schlenkflask a clear solution containing 3.49 g of LAH in 120 mL of Et₂O wastransferred dropwise via cannula over 2 h to a round-bottom 500 mLstorage flask fitted with teflon valve joint, which contained 3.46 g ofZr(BH₄)₄ dissolved in 100 mL of Et₂O and the reaction was performed inthe same manner as synthesis of material 1. Following the initialreaction, the flask was then taken into a glovebox, and a black powdermaterial was centrifuged out of the slurry using a benchtop centrifugeinside the glovebox. The black powder was then washed three times with80 mL portions of Et₂O by mixing the powder and the Et₂O using a Pasteurpipette and centrifuging the material back out of the slurry. Thematerial was then placed into a vacuum bulb and dried at roomtemperature (RT) under dynamic vacuum overnight to ˜200 torr, producing5.25 g of black powder material 2.

Example 3

Passivation of material 1 with glycerol to make material 3—1.51 g of 1was mixed with 5 mL of glycerol in a 100 mL Schlenk flask with aground-glass stopper. It was then placed on a Schlenk line and the flaskwas heated overnight in a paraffin oil bath to 125° C., initiallyproducing visible bubbling, which eventually subsided. The material wasthen cooled to RT and washed with ethanol (EtOH) in air and spun down ina benchtop high-speed centrifuge. The product black powder was driedunder dynamic vacuum at 40° C. producing 1.67 g of product black powder3.

Example 4

Passivation of material 2 with glycerol to make material 4—1.03 g of 2was placed in a 20 mL vial and mixed with 2 mL of glycerol by manualagitation. Upon mixing with the glycerol the material formed a blacksuspension which was visibly gently frothing. The foaming subsided after1 h, and the vial containing the slurry was heated to about ˜50° C. Thereaction began to foam vigorously, which necessitated the transfer ofapproximately half of the reaction to a second 20 mL vial. The vialswere allowed to stand at ˜50° C. for two days after which they weretaken out of the glovebox, and portions of EtOH were added to them towash away the glycerol. The material visibly reacted with the EtOHproducing bubbling. After three EtOH wash and centrifugation cycles thebubbling was no longer noticeable. 1.30 g of black powder material 5 wasrecovered after drying under dynamic vacuum overnight, and taken intothe glovebox for storage.

Example 5

Passivation of material 2 with D-sorbitol to make material 5—In theglovebox, 372 mg of powder 2 was mixed with ˜1.5 g of D-sorbitol powderin a 50 mL beaker and gently heated on a hot-plate until melting of thesorbitol was observed. The entirety of the contents of the beaker wasallowed to melt while the suspension was manually agitated to mix itthoroughly. The liquid was visibly frothing and was allowed to stand onthe hotplate overnight at ˜110° C. Immediately following, ˜2.5 g ofglycerol was added to the mixture and stirred in with a spatula. Theblack suspension was then allowed to cool to RT and taken out of theglovebox, after which 10 mL of EtOH was added and mixed into thesuspension. This produced mild but visible bubbling, indicating areaction of EtOH with the particles. The material was repeatedly washedwith 40 mL portions of EtOH and spun down in a benchtop centrifuge inorder to remove any remaining excess sorbitol and glycerol. The materialwas then dried at RT under dynamic vacuum overnight producing 433 mg ofproduct black powder 5.

Example 6

SEM—The particles that were observed by SEM showed a wide distributionof sizes. The SEM images of materials 3, 4, and 5 were significantlylimited with blurring occurring at higher magnifications due to chargingon the surface of the particles, as would be expected from particlesthat are non-conductive (see FIG. 1).

Example 7

TEM—TEM images of sample 3 suggest that it is a material made up of amixture of particles that are heterogeneous in size, with the bulk of itmade up of larger particles with diameter on the order of hundred(s)nanometers, which contain a core with a diameter of about half the totalparticle's diameter that is made up of a zirconium and aluminum material(FIG. 2). These cores are encased in cocoon-like shells made up ofaluminum alkoxides. EDS performed on the central dark portion of thelarge particle seen on the top in FIG. 2 exhibited peaks for Al and Zralmost exclusively, while the surrounding material that appears to beamorphous exhibited peaks for Al, C, and O.

As seen in the center and bottom images of FIG. 2, there is TEM evidenceof much smaller nanoparticles that range from 1.8 nm to 7.4 nm indiameter. Crystal lattice fringing is observed for these nanoparticlesin the TEM images with d-spacings of 2.08, 2.10, 2.19, and 2.21 Å, whichdo not match any oxide or hydride phases of Al and Zr, however, thereare mixed Zr—Al alloy phases that have peaks in the observed range,suggesting that the small nanoparticles are probably Zr—Al alloys (JCPDSRef. #s 13-510, 16-75, 17-891). Any attempts to perform EDS on theseparticles were unsuccessful due to their small size.

Example 8

Microanalysis and oxygen bomb calorimetry—The microanalysis results frommaterials 1-5 are shown in Table 1. The passivated materials to beanalyzed were shipped under air, while the unpassivated materials wereshipped under helium. The results for C, H, and N are reported as anaverage of two trials no more than 0.10% different from one another.

TABLE 1 Microanalysis results for materials 1-5 Material % C % H % N %Al % Zr R R/% C 1 2 7.03 2.01 0.59 46.42 39.24 4.71 0.67 3 13.94 1.900.58 40.27 34.02 9.29 0.67 4 10.95 2.59 0.096 5 4.35 1.27 trace 49.5841.91 2.89 0.66

The metal content for the samples was determined by atomic absorption(AA). Column R (remainder) in Table 1 gives the value of the remainderfrom 100%, presumed to be O content as supported by the constant ratioof R to % C for the passivated samples 3-5 (last column of Table 1).From these results it is apparent that materials 3, 4, and 5 arepassivated against short-term (several days) air degradation.Furthermore, material 5 was stored in air for 15 days prior to beingshipped for microanalysis, and it still exhibits the best mass ratio ofmetal to passivator (organic portion).

According to the CRC Handbook of Chemistry and Physics, the heats ofcombustion of Zr and Al metals in O₂ are 2.9 kcal/g and 7.4 kcal/g,respectively. Since carbohydrates have been used as passivating agentand when burned carbohydrates yield approximately 4 kcal/g, it wouldfollow that the nanoparticles should fall somewhere between 2.9 and 7.4kcal/g. The results from oxygen bomb calorimetry for materials 2-5 arereported in Table 2, with the reported ΔH_(obs) values being theobserved heat output, and not the actual. (The actual ΔH values were notobtained due to the material reacting with O₂ prior to ignition.)

TABLE 2 Oxygen bomb calorimetry data for materials 2-5 # ConditionsΔH_(obs) (kcal/g) 2 @ 30 atm O₂ 1.48 3 @ 30 atm O₂ 4.01 4 @ 30 atm O₂4.34 5 @ 30 atm O₂ 3.56 5 @ 40 atm O₂ 2.11 5 in paraffin wax @ 40 atm O₂2.01 5 aged 24 h in dH₂O @ 40 atm O₂ 4.61

From the calorimetry data it is evident that the unprotected particlesof material 2 are mostly oxidized before ignition occurs, as compared tothe protected materials 4 and 5, which were made from 2. Anotherinteresting observation is the difference in combustion energy outputobserved for material 5 when combusted at 30 versus 40 atm of O₂. Thesignificantly lower energy output at the higher pressure confirms thateven when passivated, the material reacts with O₂ prior to ignition.These previous calorimetry experiments were conducted in the presence ofa known amount of ethylene glycol or glycerin, however, another attemptwas made to obtain calorimetry data from material 5 by embedding it intoparaffin wax; however, that yielded the same results as with ethyleneglycol, showing that paraffin is inadequate at protecting the particlesfrom 40 atm of O₂. Probably the most surprising result from calorimetrywas the energy output observed for material 5 after it was dispersed inwater for 24 h. The material was suspended in water and allowed to standovernight as an experiment to observe how it would settle out, as seenin FIG. 3. The observed heat output from the water-treated material 5was actually higher than for the same material before water treatment,suggesting that water reacts with the material's surface at leastpartially preventing O₂ from spontaneously reacting with particles. Thisis also supported by the observation of a slight evolution of gasbubbles when the particles were mixed with water. These results showthat material 5 contains at least 4.61 kcal/g.

Example 9

²⁷Al Magic Angle Spinning NMR—From magic angle spinning experiments itwas found that the unpassivated nanoparticle materials are electricallyconductive, since they were producing eddy currents counteracting theinstrument's magnetic field thereby resisting spinning. On the otherhand, the passivated materials were found to be non-conductive and hadno problem spinning.

Initial magic angle spinning ²⁷Al-NMR experiments have shown that thereare two main peak regions for the Zr—Al nanoparticle materials, with theAl metal peak at 1646 ppm (relative to Al³⁺ in H₂O) and the Al non-metalpeaks have been observed in the 0-100 ppm region. As shown in FIG. 4,the unpassivated material exhibits a much smaller non-metal Al peak,whereas the passivated material has a significant non-metal Al peak.

Example 10

Synthesis of Hf—Al-nanoparticle material from Hf(BH₄)₄ and LAH—From a200 mL Schlenk flask a clear solution containing 3.77 g of LAH in 120 mLof Et₂O was transferred dropwise via cannula over 2 h to a round-bottom500 mL storage flask fitted with teflon valve joint, which contained5.90 g of Hf(BH₄)₄ dissolved in 100 mL of Et₂O while cooled to 0° C. andthe reaction was sonicated overnight producing a black slurry. Followingthe initial reaction, the flask was then taken into a glovebox, and ablack powder material was centrifuged out of the slurry using a benchtopcentrifuge inside the glovebox. The black powder was then washed threetimes with 80 mL portions of Et₂O by mixing the powder and the Et₂Ousing a Pasteur pipette and centrifuging the material back out of theslurry. The material was then placed into a vacuum bulb and dried at120° C. under dynamic vacuum overnight to ˜200 torr, producing 7.08 g ofblack powder material.

Example 11

Ti—B particles—TiCl₄, LiBH₄, and LiAlH₄ were reacted as shown in FIG. 5.The LiCl impurity was removed from the collected powder by washingnumerous times with tetrahydrofuran (THF) to maintain room temperatureprocessing conditions, in contrast to removing the LiCl by hightemperature vacuum sublimation. {Bates, 1995 #203} The collected powderswere heat treated under dynamic vacuum at 150° C., 450° C., and 720° C.to investigate any changes in crystallinity, reactivity, and morphology.From a crystallographic standpoint, the as-prepared powder as well asthose heat treated at 150° C. and 450° C. were amorphous. The sampleheat treated at 720° C. showed weak diffraction with d-spacingsresembling a TiB₂ crystal phase (FIG. 6). The calculated crystallitesize for the TiB₂ phase was 1.44 nm, based on peak widths. Theoccurrence of the TiB₂ phase upon high temperature annealing iscommensurate with previous works. {Bates, 1995 #203}

While heat treatment induced crystallinity, there was little effectobserved on the overall particle size and shape of the Ti—B powders(FIG. 7). Primary particle diameters ranged from 100 nm-1 micron,possessing smooth surfaces with stochastic elliptical morphologies;secondary particle diameters ranged from 10 to hundreds of microns indiameter. Heat treating at higher temperatures resulted in no observableprimary or secondary particle growth. The high degree of agglomerationwitnessed for each sample has been previously reported for similarsyntheses, and can be attributed to a lack of any strong surfacecoordinating or sterically hindering molecules used during thesynthesis. {Epshteyn, 2013 #215} Diethyl ether, the solvent used, is aweakly coordinating solvent with minimal steric effects. Halide ions arereported to have shape and size directing capabilities; however the LiClformed during the exchange of BH₄ ⁻ for Cl⁻ has poor solubility indiethyl ether and would preclude significant Cl⁻ presence in solutionand any possible halide ion effect on size or shape. {DuChene, 2013#264; Lohse, 2014 #265}

Even though the ethereal solvents used are weakly coordinating, solventcoordination and activation can introduce contaminants during sampleannealing. {Epshteyn, 2009 #260; Epshteyn, 2013 #215} Thermogravimetricanalysis (FIG. 8) coupled with mass spectrometry (FIG. 9) (TGA-MS) ofthe evolved gases under a 60% 02 atmosphere was used to identifycontaminants. The as-prepared powders were pyrophoric when exposed toair and were not analyzed using this method. Powders heat treated at150° C. displayed an initial sharp oxidation concurrent with a weightincrease at 500° C. MS signal for CO₂ and H₂O (m/z=44 and 18,respectively) were detected during this initial oxidation and isattributed to desorption of surface coordinated ethereal solvent. Above500° C., a slow gradual weight increase occurs with no observable MSsignal. Powders annealed at 450° C. also showed a sharp, initialoxidation around 500° C. and release of CO₂. However, a second releaseof CO₂ was observed above 700° C. and can be attributed to thedecomposition of a TiC phase. {Vallauri, 2008 #263; Biedunkiewicz, 2011#261; Shen, 2007 #262} Powders heat treated at 720° C. also showed theevolution of CO₂ at high temperatures, implying the presence of a TiCphase.

Differential Scanning calorimetry (DSC) (FIG. 10) heat release valuesduring heating under a 60% 02 atmosphere where commensurate with massgains witnessed in TGA traces. Heating at a rate of 25° C. min⁻¹ causedpowders heat treated at 150° C. and 450° C. to display a sharpexothermic event at 513° C. and 522° C., respectively. Powders heated at720° C. showed a less intense, broader heat release beginning at 500° C.and persisting above 600° C. The observed exothermic events are due tothe oxidation of the Ti and B metals to their more stable oxide forms.Slower heating rates resulted in the oxidation process occurring over abroader range of temperatures; however, for each heating rate theinitiation of oxidation occurred at the lowest temperature for powdersannealed at 150° C. and highest for powders annealed at 720° C.

From the collected DSC traces, the exothermic peak maxima were used toconstruct Kissinger Plots allowing for the calculation of the activationenergy for thermo-oxidation. {Kissinger, 1957 #267} Powders heat treatedat low temperatures showed the lowest activation energy, implying thatpowders are more reactive with lower heat treating temperatures. Forcomparison, the calculated activation energies for the prepared Ti—Bpowders were evaluated against commercially available Ti and B powders.The activation energy for oxidation for commercial Ti and B powders were265 and 145 kJ/mol; which aligns well with reported literature values.{Kofstad, 1957 #225} The higher activation energy of the as preparedTi—B powders implies that they are more stable against thermo-oxidation.

While stability against oxidation results in a material that is safer tostore and handle, the efficiency and quantity of energy release is themost pertinent metric for any energy storage material. Thus, oxygen bombcalorimetry was used to access the energy storage capacity of preparedTi—B powders, with the results shown in Table 3. Elemental Ti and B areexpected to release 20 kJ/g and 58 kJ/g upon combustion, respectively.{Dreizin, 2009 #50} The value measured for pure commercial Ti powderswas 19.75 kJ/g, very close to the expected value. The value measured forcommercial boron powders is quite lower than expected; boron is wellknown to have poor combustion efficiency. {Ao, 2014 #61}. Theoretically,a mixture of a Ti atom and 2 B atoms should release 31.17 kJ/g, andcrystalline TiB₂ is expected to release 27.15 kJ/g upon combustion.{Trunov’, 2008 '#192} Looking at Table 3, the prepared Ti—B powder thatwas not heat treated released 33.17 kJ/g; a value higher than expectedfor a powder containing a TiB₂ stoichiometry. With increasing heattreatment temperatures, powders showed a decrease in energy stored.

TABLE 3 Calorimetric properties of synthesized Ti—B powders Heat ofcombustion Activation energy Sample ID (kJ/g) (kJ/mol) Ti—B as prepared33.17 n/a Ti—B annealed at 150 C. 29.80 337.25 Ti—B annealed at 425 C.26.30 402.41 Ti—B annealed at 720 C. 23.67 418.63 Commercial Ti powder19.75 265.62 Commercial B powder 21.77 145.43

As shown in the XRD and TGA results, mixtures of Ti, B, and C formstable TiC and TiB₂ crystal phases when heated. TiC and TiB₂ crystalphases are exothermic phases, meaning that they release energy in theform of heat upon formation. The formation of TiC and TiB₂ crystalphases release 3.07 kJ/g and 4.02 kJ/g, respectively. {Humphrey, 1951#240; Trunov, 2008 #192} Hence, the decrease in energy output withincreased heat treatment temperature can be attributed to the formationof TiC and TiB₂ phases. However it is unlikely that heat treating at150° C. would induce alloy formation; TiC and TiB₂ phases are veryrefractory in nature. {Rudneva, 2007 #206} The relatively large decreasein heat output between the as prepared powders and those heated to 150°C. can be attributed to the release of volatile borohydrides, as shownin FIG. 11. The as prepared Ti—B powders lose 7.67% mass upon heating to500° C.; this mass loss results in a significant MS signal for B₂H₆(m/z=26). The majority of mass loss occurred between 100° C. and 250°C., which is commensurate with the reported decomposition temperature of200° C. for Ti(BH₄)₃. B₂H₆ releases 73.48 kJ/g of heat upon combustionto form B₂O₃ and H₂O; hence by retaining boron and hydrogen, an 11%increase in combustion energy is measured between the as prepared Ti—B—Hpowders and powders heat treated at 150° C. It should be emphasized thatthe bomb calorimetry energies in Table 3 and TGA-MS data in FIG. 11 werecollected several months after the initial synthesis, demonstrating thelong term stability of the Ti—B—H composite powders.

Many modifications and variations are possible in light of the aboveteachings. It is therefore to be understood that the claimed subjectmatter may be practiced otherwise than as specifically described. Anyreference to claim elements in the singular, e.g., using the articles“a,” “an,” “the,” or “said” is not construed as limiting the element tothe singular.

What is claimed is:
 1. A nanopowder made by a process comprising:reacting Ti(BH₄)₃ with LiAlH₄ in an aprotic solvent while beingsonicated to produce nanoparticles comprising titanium, boron, andhydrogen; wherein the molar ratio of Ti(BH₄)₃ to LiAlH₄ is from 1:1 to1,000,000:1; and annealing the nanoparticles under a vacuum.
 2. Thenanopowder of claim 1, wherein the molar ratio of Ti(BH₄)₃ to LiAlH₄ isfrom 1:1 to 12:1.
 3. The nanopowder of claim 1, wherein the aproticsolvent is diethyl ether.
 4. The nanopowder of claim 1, wherein thesonication is performed at −15° C. to 97° C.
 5. The nanopowder of claim1, wherein the annealing is from 50° C. to 2000° C.
 6. The nanopowder ofclaim 1, wherein the nanopowder comprises at least 90 wt. % elementalamorphous titanium and elemental amorphous boron.
 7. The nanopowder ofclaim 6, wherein the nanopowder comprises no more than 5 wt. % of totalcrystalline titanium or boron, alloyed titanium and boron, andtitanium-boron compounds.